JPS6036577A - Composition useful for curable coating - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION BACKGROUND OF THE INVENTION This invention relates to reaction products of polyols, multifunctional incyanates, lactone-acrylate adducts, and optionally hydroxyalkyl acrylates. These compositions are suitable for use in curable coatings.

Invention The inventors have discovered that a composition comprising a reaction product of a polyol, a polyfunctional incyanate, a lactone acrylate adduct, and optionally a hydroxyalkyl acrylate is suitable for use as a radiation-curable coating composition. I found it.

This composition exhibits desirable low viscosity while providing good physical properties for radiation cured coatings.

Substantially any of the organic materials conventionally used in the art for preparing coating compositions can be used in the present invention. Examples of polyols useful in preparing coating compositions in accordance with the present invention include polyether polyols such as polyhydroxyalkane and hyperoxyalkylene polyols, acrylic acid polyols, vinyl polyols, polyester polyols, polyvalerolactone. Polyols and other lactone polyols, such as polyvalerolactone polyol, polymethylcaprolactone polyol, etc., as well as polymers/polyols. Among the polyether polyols that can be used are selected from one or more of the following classes of compositions known to those skilled in the art, alone or in mixtures: (a) Fullylene oxide adducts of polyhydroxyalkanes; (b) alkylene oxide adducts of non-reducing sugars and sugar derivatives; (C) alkylene oxide adducts of phosphorous acid and polyphosphorous acids; (d) alkylene oxide adducts of polyphenols; (e) such as castor oil; polyols from natural oils.

Examples of alkylene oxide adducts of polyhydroxyalkanes include ethylene glycol, propylene glycol, 1,3-dihydroxypropane, 1,3
-dihydroxybutane, 1,4-dihydroxybutane,
1,4-11,5-1 and 1,6-cyhydroxyhexane, l, 2-11,3-11,4-11,6-1 and 1
, 8-dihydroxyoctane, 1,10-dihydroxydecane, glycerin, 1,2゜4-trihydroxybutane, 1,2,6-trihydroxyhexane, t, l, 1
−)! l-methylolethane, 1.1.1-)limethylolpropane, pentaerythritol, polycaprolactone, xylitol, arabitol, sorbitol, and alkylene oxide adducts of mannitol. A preferred class of alkylene oxide adducts of polyhydroxyalkanes are adducts of trihydroxyalkanes with ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof.

Yet another class of polyether polyols that can be used are alkylene oxide adducts of non-reducing sugars in which the alkylene oxide has 2 to 4 network atoms.

Among the non-reducing sugars and sugar derivatives contemplated are sucrose; methyl glucoside; alkyl glucosides such as ethyl glucoside; ethylene glycol glucoside, propylene glycol glucoside, 1,2,6-hexanetriol glucoside, etc. a7. Glycol glycooxides; and alkylene oxide adducts of alkyl glycosides as described in U.S. Pat. No. 3,073,788. ．． ).

Phosphous acid and alkylene oxide adducts of polyphosphorous acid are another useful class of polyether polyols. Ethylene oxide, 2-epoxypropane, epoxybutane, 3-chloro-1,2-epoxypropane, and the like are preferred alkylene oxides. In this connection it is desirable to use phosphoric acid, phosphorous acid, polyphosphoric acids such as tripolyphosphoric acid, polymetaphosphoric acids and the like.

Yet another useful class of polyether polyols are polyphenols, preferably alkylene oxide adducts of those polyphenols, where the alkylene oxide is an alkylene oxide having from 2 to 4 carbon atoms. Among the polyphenols contemplated are, for example, bispheno-A/A1 bisphenol r1 condensation products of phenol and formfuldehyde, novolak resins, condensation products of various phenolic compounds and acrolene, the most important of this class being The simplest ones are 1,1°3-tris(hydroxyphenyl)pro/kne, condensation products of various phenolic compounds with glyoxal, glutaraldehyde and other dialdehydes, the simplest of this class. (Yo1.1.2.2-tetrakis(
Hydroxyphenol) ethane, etc.

The polyols described above may have hydroxyl numbers that vary over a wide range.

Generally, the hydroxyl number of the above-described polyols used in the present invention can range from about 15 and below to about 900 and above.

Hydroxyl number is defined as the number of milligrams of potassium hydroxide required to completely neutralize a fully phthalated derivative prepared from 1 g of polyol. The hydroxyl number can also be defined by the equation: (wherein OH - the hydroxyl number of the polyol; f - the functionality, i.e. the average number of hydroxyl groups per molecule of the polyol; and m, w, = molecular weight of the polyol) . The polyether polyols described above can be made by conventional methods and are commercially available from a number of manufacturers.

Polycaprolactone polyols, alone or as admixtures, which can be used to prepare the coating compositions of the present invention include those commercially available and those described in detail in, for example, U.S. Pat. No. 3,169,945. It includes any known polycaprolactone polyol. As described in the above patent specification ■, the polycaprolactone polyol contains an excess of caprolactone and at least 2
It is produced by ring-opening polymerization with an organic polyfunctional polymerization initiator having reactive hydrogen atoms. The organofunctional polymerization initiator may be any polyhydroxy compound as shown in the aforementioned US Pat. No. 3,169,945.

Examples of these include ethylene glycol, diethylene glycol, triethylene f-1-, A-1x,
z-furopylene glycol, dipropylene glycol,
1.3-Flopylene gelicol, polyethylene glycol, polypropylene glycol, poly(oxyethylene-oxypropylene) glycol, neomenthyl glycol, 1,4-cyclohexane dimetatool, 2,4□
4-trimethyl-pe/tanediol, 2,2-dimethyl-3-hydroxypropyl 2,2-dimethyl-3-hydroxyprobionate and similar molecules containing about 4
Polyalkylene glycols, either blocked, capped or with petero atoms, with up to 0 or more alkyleneoxy degrees, 3-methyl-1-5-bentanediol, cyclohexanediol, 4.4'- Methylene-bis-cyclohexanol, 4,4'-impropylidene bis-cyclohexanol, xylene diol, 2-(4-hydroxymethylphenyl)ethanol, 1,4-butanediol, 1,6
- Diols such as hexanediol, etc.; triols such as glycerin, trimethylolpropane, 1,2,6-hexanediol, triethanolamine, triisopronoquinolamine, etc.; erythritol, pentaerythritol, N, N, N There are tetrols such as ',N'-tetrakis(2-hydroxyethyl)ethylenediamine and the like.

When an organofunctional polymerization initiator is reacted with caprolactone, a reaction occurs that can be expressed in its simplest form by the following equation: In this equation, the organofunctional polymerization initiator is 几, (O
H) A compound in which caprolactone is a compound of ε-caprolactone itself or a substituted caprolactone (in which case U.S. Pat.
As shown in No. 45, R' is an alkyl, alkoxy, aryl, cycloalkyl, alkaryl or aralkyl group containing up to 12 carbon atoms, and at least 6 R' groups are hydrogen atoms. can be). The polycaprolactone polyols used are shown by the formulas on the right side of the above equation and can have an average molecular weight of 200 to about 6000. Preferred polycaprolactone polyol compounds have an average molecular weight of about 290 to about 6,000. Most preferably about 290-30
00. Most preferred are polycaprolactone diol compounds having an average molecular weight of about 290 to about 1500 and an average molecular weight of about 290 to about 300.
These are polycaprolactone triol and polycaprolactone tetrol compounds having 0. In the above formula, m is an integer representing the average number of repeating units necessary to produce a compound having the above molecular weight. The hydroxyl number of the polycaprolactone polyol is about 15 to 6.
00, preferably 200 to 500, and the polycaprolactone has an average of 2 to 8 hydroxyl groups,
Preferably, it can have 2 to 4 pieces.

Polycaprolactone polyols that can be used in the coating composition of the present invention include polyhydroxyl metal having an average of 2 to 6 hydroxyl groups and caprolactone polyols having an average of 2 to 6 hydroxyl groups.
Mention may be made of reaction products with chthons. A method for producing these types of polycaprolactone polyols is shown in the aforementioned US Pat. No. 3,169,945, and a number of such compositions are commercially available. The table below shows exemplary polycaprolactone polyols.

The first column of the table shows the organic functional polymerization initiator that reacts with caprolactone, and the second column shows the average molecular weight of the polycaprolactone polyol. Knowing the molecular weights of the polymerization initiator and polycaprolactone polyol, it is possible to easily determine the average molecular weight (cpz, unit) of caprolactone that produces the compound in reaction l-.

This value is shown in No. 31R.

Polycaprolactone polyol 1 Ethylene glycol 2902 2 Ethylene glycol 803 6.53 Ethylene glycol 2,114 184 Propylene glycol 8747 Mu Octylene glycol 6024 6 Decalene glycol 801 5.57 Diethylene glycol 527 L78 Diethylene glycol 847 6.59 Diethylene glycol 1.2 4
6 1010 Diethylene glycol 1,998 1
6.611 Diethylene glycol 3.526 30
12 Triethylene glycol 754 5.313 Polyethylene glycol G±molecular weight 200) 713 4.
514 Polyethylene glycol * 1,3 8 7
Coating amount 600) 15 Polyethylene glycol * 2,868 12
ω molecular weight 1500) 16 1.2-propylene glycol 6465171
．． 3-Propylene glycol 988818 Dipropylene glycol 476 319 Polypropylene glycol * 835 3.6 (molecular weight 425) 22 HexyV:yfs=i -# 916 7232
-Ethyl-1,3-hexanediol 602 424
1.5-bentanediol 4463251.4-cyclohexanediol 029 4-5n glycerol 548 4 28'l, 2.6-hexanediol 476 3w
Trimethylolpropane 5904 blade Trimethylolpropane 750 5.431 Trimethylolpropane 1,103 8.532 Triethanolamine 89
0 6.5 Erythritol 920 7 Pentaerythritol 1,219 9.535
1.4-Butanediol 546 4.036 Neopentyl Glycol 674 5.0 Average Molecular Weight of Glycols The structures of the compounds in the above table will be clear to those skilled in the art based on the information provided. The structure of the seventh compound is idealized as (where the variable r is an integer), r
The sum of + r has an average value of 3.7 and the average molecular weight is 5
It is 27. The structure of the 20th compound is idealized as i, where the sum of r + r has an average value of 6 and the average molecular weight is 1684. This explanation provides clues to the structural formulas of compounds 1 to 34 shown above.

Polycaprolactone hexols suitable for use in the present invention can be prepared by catalytic polymerization of excess polycaprolactone polyol and a cycloaliphatic epoxide. Examples of polycaprolactone polyols useful in preparing polycaprolactone hequinol include polycaprolactone diol, polycaprolactone triol, and mixtures thereof. Many of these polycaprolactone polyols are commercially available from Union Carbide. Cycloaliphatic epoxides suitable for use in the preparation of polycaprodictonehexol include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis(3,4-
epoxycyclohexylmethyl) adipate, vinylcyclohexene dioxide, and the like. Many of these cycloaliphatic epoxides are commercially available from Union Carbide. A preferred polymerization catalyst is 3M as FC-520.
It is diethylammonium tri7late commercially available from Co., Ltd.

The preferred method for producing polycaprolactone hexol is 1
Seed or more polycaprolactone triol is added to the reactor and the polycaprolactone )! J;t-
heating the polycaprolactone triol to a temperature of about 20° C. and adding the catalyst using nitrogen blowing as soon as the polycaprolactone triol has melted. The mixture of polycaprolactone triol and catalyst is heated to a temperature of about 50°C to about 200°C, and then the cycloaliphatic epoxide is added to the mixture. The reaction is carried out for about 1 hour to about 3 hours or until the oxirane content is reduced to zero or nearly zero values. Modifications to this method can include adding all ingredients to the reactor first. Yet another modification of this method is that after addition of the catalyst,
This can include vacuuming for 30 minutes and/or using vacuum while heating the polycaprolactone triol to a molten state. A preferred polycaprolactone hequinol suitable as a component of the coating composition of the present invention has an average molecular weight of about 600 to about 1500.

The polymers/polyols that can be used to prepare the coating compositions of the invention are known materials. Such polymers/polyols can be prepared by polymerizing one or more ethylenically unsaturated monomers dissolved or dispersed in the base polyol in the presence of a free radical catalyst. For the production of polymers/polyols, see U.S. Re. 28,715 and U.S. Re. 29.11.
No. 8, U.S. Pat.
No. 236, No. 4.172, No. 825 and No. 4.19 of the same
8.488 each specification in more detail.

Although poly(oxypropylene) polyol is preferred as the base polyol, virtually any polyol conventionally used in the art for making polymers/polyols can be used. Examples of base polyols useful in making polymer/polyol compositions are polyether polyols or the like, such as polyhydroxyalkanes and polyoxyalkylene polyols. Among the basic polyols that can be used are one or more, alone or in admixture, selected from the following classes of compositions, known to the person skilled in the art and described in more detail above: There are: (a) alkylene oxide adducts of polyhydroxyalkanes; (b) alkylene oxide adducts of non-reducing sugars or sugar derivatives; (C) alkylene oxide adducts of phosphorous acid and polyphosphorous acids; (d) polyphenols. (e) polyols from natural oils such as castor oil etc. The most preferred base polyols for use in the polymers/polyols useful as components of the coating compositions of the present invention are poly(oxypropylene) polyols. include. It should be appreciated that polymer/polyols can be prepared using mixtures or blends of more than one base polyol if desired.

Conceptually, the monomers 1m) used in the preparation of the polymer/polyol can include any ethylenically unsaturated monomer. A variety of monomers are disclosed in the above-mentioned polymer/polyol patent specifications. The selection of monomer(s) used will depend on such considerations as the relative cost of the monomers and the properties of the product required for the intended use.

Preferred monomers and monomer mixtures used to prepare the polymer portion of the polymer/polyol are acrylonitrile and a mixture of acrylonitrile and styrene, respectively. The relative weight proportions of acrylonitrile to styrene can range from about 80:20 to about 20:80.

In some applications, it may be desirable to use comonomers other than styrene with acrylonitrile. Representative examples of suitable comonomers include methyl methacrylate, vinyl chloride and vinylidene chloride.

The polymer and polyol content of the polymer/polyol is
It can be varied within wide limits depending on the requirements of the intended end use. Generally the polymer content is from about 10 to about 50% based on the weight of the polymer/polyol.
Varies over 0.

The polyol content of the polymer/polyol varies from about 50 to about 90% based on the weight of the polymer/polyol.

If desired, the polymer/polyol can be mixed with conventional polyols other than those previously described above to reduce the polymer content to the level desired for the particular end use. The resulting polymer content is 4% of the total weight of the mixture.
% or even less may also be useful in the coating compositions of the present invention.

Preferred fll used in the coating composition of the present invention
The polyols of ii are TONE-0200 and TONE 03, both commercially available from Union Carbide.
Polycaprolactone polyols such as Polycaprolactone polyols such as Polymeg 05;
) dihydroxyl functional polytetramethylene oxide polyols such as 650.1000 and 2000;
yol) 31-23 and 34-28/
polyols, and adducts of ethylene oxide and propylene oxide, including of course ethylene glycol, diethylene glycol, poly(oxyethylene) glycol, poly(oxypropylene) glycol, poly(oxypropylene) triol; IIJtT-67, L, commercially available from Union Carbide Co.
Higher functionality polyols such as HT-112 and LG-56. Although these polyols also include poly(oxypropylene-oxyethylene) polyols, it is desirable that the oxyethylene content constitutes 80% or less, preferably 60% or less of the total.

Ethylene oxide, if used, can be incorporated in any manner along the polymer chain.

In other words, ethylene oxide is an internal block and propylene oxide polyol capped with ethylene oxide, i.e., Niax Vorio/I/11-27 and 11-34, commercially available from Union Carbide Corporation.
and E-474, or can be randomly distributed along the polymer chain. As is well known in the industry,
The most preferred polyols in this case have varying amounts of unsaturation. Unsaturation per se has no adverse effect on the formation of the coating composition of the present invention.

Other preferred representatives of organic polyols that can be used in the coating compositions of the present invention include acrylate esters, vinyl halides, hydroxypropyl and hydroxyethyl acrylates and methacrylates and other free radical polymerizable organic polyols. , vinyl acetate or copolymers with monomers such as styrene; polyvinyl acetals with pendant hydroxyl groups of copolymers with pendant hydroxyl groups produced by hydrolysis or partial hydrolysis of vinyl acetate copolymers. Resins; modified cellulose polymers such as hydroxyethylated and hyhydroxyfurobylated cellulose; hydroxy-terminated polyesters, hydroxy-terminated polyalkadienes and styrene alkyl alcohol copolymers. Polyester polyols are reaction products of polyfunctional organic carboxylic acids and polyhydric alcohols, such as poly(hexamethylene adipate), poly(ethylene adipate), poly(butylene adipate), etc.
etc. Many of these organic polyols can be prepared by conventional methods and are available from Vutvar E-72A, 13-73, B-
76, B-90 and B-98 as well as Formvar 7/70.

Polyvinyl acecool resins commercially available from Monzant Chemical Company as 12/85.7/958, 7795B, 15/958 and 1,5/95E; commercially available from Rohm and Haas Company as Paraplex V-148 aliphatic polyester diol; Multron R-2,
几-12AlR-16, R-18, 几-38, R-68
and R-74 from Mobay Chemical Company; Klucel
) Hydroxyprobylated cellulose having an equivalent weight of about 100, commercially available as E from Hercules; cellulose acetate butyrate ester having a hydroxyl equivalent weight of about 400, commercially available from Eastman Kodak as alcohol-soluble butyrate; commercially available from the manufacturer.

Another preferred class of polyols for use in the present invention are those having a molecular weight of less than about 3000 and produced from the open type polymerization of lactones with a multifunctional polymerization initiator, in which polyester/l The minimum % y of lactone hydroxyls in the /polyol (i.e. those hydroxyls attached to ring-opened lactones) is a function of the molar ratio X of lactone units to active hydrogen in the polymerization initiator, where y for =52.5x and x>
1.5, it can be defined as y=2.11 x+75.6.

Polyester polyols are produced by ring-opening reactions of lactones using polyfunctional polymerization initiators.

A preferred lactone is ε-caprolactone.

The polymerization amount f'8 agent has the formula: % formula %) [wherein is an organic group selected from the group consisting of aliphatic, cycloaliphatic, aromatic and heterocyclic groups, and a is the polymerization The number is equal to the functional number of the initiator, and the sword is -0-l-NH
-1-NR2- (R2 is selected from alkyl, aryl, aralkyl or cycloalkyl), -8-1 and -a(o)o-].

The type of B 2 H group in the sole polymerization initiator can be the same as in aminoalcohol hydroxylcarboxylic acid, etc., or it can be varied.

A preferred polymerization initiator is an organic polyol in which the BII group is a hydroxyl group.

The molecular weight (number average, Mn) of the polyol product is approximately 30
00 or less, preferably about 1500 or less.

The reaction between the lactone and the polyfunctional polymerization initiator is preferably carried out in the presence of a catalyst.

Catalysts that can be used include 1 fl or more of organometallic compounds and other metal compounds such as stannous chloride, other Lewis acids, and proton hydroxides. Preferred catalysts include stannous ophthonic acid, digtyltin laurate and other tin compounds; titanates such as tetrainfurobyl titanate and butyl titanate, and the like. Any catalyst commonly used for ring-opening polymerization of lactones can be used in the practice of this invention.

The catalyst is about 0.1-50 based on the total R of lactone.
used in the customary amounts of pT)m.

The reaction can be carried out in a solvent, but the solvent must be free of active hydrogen groups, such as hydrocarbon solvents. Preferably, the reaction is carried out in a pure state, without the presence of any solvent.

Although the reaction can be carried out at atmospheric pressure, higher or lower pressures can also be used.

The reaction is carried out at about 100 to about 200°C, preferably about 140°C.
to about 170°C.

The reaction is carried out over a period of about 1 to about 24 hours, preferably about 3 to about 8 hours. It is important to avoid prolonged reaction times and excessive reaction temperatures that would result in a gradual decrease in the percentage of lactone hydroxyl groups.

The organic polyol used in the coating composition of the present invention can be a mixture or admixture of organic polyols. For example, polycaprolactone polyol, propylene oxide polyol when used, propylene oxide polyol capped with ethylene oxide,
It may be desirable to mix or blend the polycaprolactone polyol with one or more polytetramethylene oxide polyols or monomer/polyols. Other mixtures and admixtures can be used as well, if desired.

Multifunctional incyanates suitable for use in the present invention are known in the art and include aliphatic and aromatic diisocyanates. Many of such compounds are well known to those skilled in the art, examples of which include 2,4-lylene diincyanate, 2,6-lylene diincyanate, 4,4' -diphenylmethane diisocyanate, di(
2-incyanatoethyl)-bicyclo(2,2,1)hept-5-ene-2,3-dicarboxylate, 3.5
．． 5-) Liethyl/l/-1-incyanato-3-isocyanato-methylcyclohexane, 1,6-hexamethylene diisocyanate, m- and p-xylene diisocyanate, cyclohexane-1,4-diisocyanate, dicyclohexyl-4, 4'-methane diisocyanate, tetramethylene diisocyanate, cyclopencarene-1,3-diyncyane), 1,3-diisocyanate, 1,4-xylene diisocyanate tale diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate , hexamethylene diinocyanate, 3,3'-dimethyl-4,4'-
diphenylmethane diisocyanate, 4.4'-diphenylmethane diisocyanate, 3.3'-dimethylbiphenylene diisocyanate, 4.4'-biphenylene diisocyanate, 3.3'-dimethoxy 4,4'-dimethyl 4.4'-biphenylene diisocyanate, durenidisocyanate, 1-phenoxy-2,4-phenylene diisocyanate, 1-1-butyl-2,4-phenylene diisocyanate, 2,2.4-) dimethylhexamethylene diisocyanate, 1. ．． Mention may be made of 3,5-benzene triisocyanate, 2,4,6-1-luentriisocyanate, etc., or mixtures thereof.

Lactone-acrylate adducts suitable for use in the present invention are prepared by reacting a lactone with a hydroxyalkyme acrylate.

Suitable lactones for use in preparing the lactone-acrylate adducts of the present invention have the following formula: (wherein R' is independently hydrogen or a carbon atom +1 to 12
4 to 7). A preferred lactone is ε-caprolactone.

Hydroxyalkyl acrylates include 2-hydroxyethyl acrylate, hydroxyalkyl acrylate, hydroxybutyl acrylate, 2-hydroxy-3-chlorofurobyl acrylate, 2,3-dihydroxypropyl acrylate, etc. or mixtures thereof. Hydroxyethyl-acrylate is preferred. Small amounts of hydroxyalkyl methacrylates may also be included.

The lactone-acrylate adduct is prepared by reacting a lactone with a hydroxyalkyl acrylate in the presence of up to about 200 ppm of catalyst. Catalysts that can be used include one or more organometallic compounds, other metal compounds such as stannic chloride or ferric chloride, and other Lewis or protic acids. Preferred catalysts include stannous ophtonate, dibutyltin dilaurate, and other tin compounds; titanates such as tetraisopropyl titanate and butyl titanate, and the like.

The reaction is carried out at about 100 to about 140°C, preferably about 120°C.
to about 130°C.

The reaction can be carried out at atmospheric pressure, but higher or lower pressures can also be used.

The reaction is generally conducted in the presence of oxygen to inhibit polymerization of the hydroxyalkyl acrylate. The reaction is conducted for about 2 to about 20 hours, preferably about 3 to about 11 hours. The reaction is carried out in the presence of a suitable inhibitor to inhibit polymerization of the hydroxyalkyl acrylate double bonds.

These inhibitors include monomethyl ether of hydroquinone, benzoquinone, phenothiazine, methylhydroquinone, 2,5-di-t-butylquinone, hydroquinone,
and other common art-known free radical inhibitors. The level of use of the inhibitor is 1000 ppm or less, preferably 800 ppm or less. The hydroxyalkyl acrylate component of the present invention is selected from those mentioned above, with hydroxyethyl acrylate being preferred.

The lactone acrylate adduct contains from about 1 to about 10 moles of lactone per mole of hydroxyalkyl acrylate.

The compositions of the invention can be made by adding the ingredients in a number of different ways. For example, the polyol, polyfunctional incyanate, lactone-acrylate adduct and hydroxyalkyl acrylate can all be added together. It is also possible to react the lactone with the hydroxyalkyl acrylate and then add the multifunctional incyanate and polyol and optionally additional hydroxyalkyl acrylate. It is also possible to react the polyol with the polyfunctional incyanate and then react this product with the dichton-acrylate adduct and optionally further additional hydroxy-alkyl acrylate and/or reactive solvent. Non-reactive solvent can be added at any point.

Preferably, the lactone-acrylate adduct is reacted with a polyfunctional incyanate, and then the product is reacted with a polyol and optionally additional hydroxyalkyl acrylate.

The reaction is generally carried out in the presence of a catalyst. Catalysts that can be used in the present invention include one or more organometallic compounds and other metal compounds, such as stannic chloride or ferric chloride, and other Lewis and protic acids. A preferred catalyst is octanoic acid.
tin, dibutyltin dilaurate, and other tin compounds; titanates such as tetraisoflovir titanate and butyl titanate; and the like. The catalyst is 0
．． 0.001 to about 5%, preferably about 0.01 to about 2%.

The reaction is carried out at a temperature of about 25 to about 150°C, preferably about 40 to about 80°C. Although the reaction can be carried out at atmospheric pressure, higher or lower pressures can also be used. The reaction is conducted for about 1 to about 72 hours, preferably about 2 to about 24 hours.

The reaction is carried out in the presence of a suitable inhibitor to prevent polymerization of the hydroxyalkyl acrylate double bonds. These inhibitors include the catalysts described above in the amounts described above.

The reaction can be carried out in the presence of reactive or conventional solvents. Preferred reactive solvents that can be used have the formula: % where X is hydrogen or methyl and 2 is substituted,
or unsubstituted alkyl, cycloalkyl, alkenyl,
Aryl or aralkyl, in which case the substituents can be alkoxy, hydroxy, cyan or amino, or R9 can be carbamoylalkyl which can be N-alkyl substituted.

Examples of suitable reactive solvents include ethyl acrylate,
Monomers having up to about 12 carbon atoms in the alkyl moiety, such as butyl acrylate, 2-ethylhexyl acrylate, amyl acrylate, n-lauryl acrylate, nonyl acrylate, n-octyl acrylate, isooctyl acrylate, isodecyl acrylate, etc. Functional alkyl acrylates; alkoxyalkyl acrylates such as methoxybutyl acrylate, ethoxyethyl acrylate, ethoxypropyl acrylate, etc.; alkenyl acrylates such as hydroxyethyl acrylate, hydroxybutyl acrylate, etc.; trimethoxyaryloxymethyl acrylate, allyl acrylate alkenyl acrylates such as; aralkyl acrylates such as phenoxyethyl acrylate, benzyl acrylate, etc.; cycloalkyl acrylates such as cyclohexyl acrylate, cyclopentyl acrylate, inbornyl acrylate, etc.; aminoalkyl acrylates such as diethylaminoethyl acrylate. 2-carbamoyloxyethyl acrylate, 2-carbamoyloxyethyl acrylate, N-methylcarbamoyloxyethyl acrylate, N-ethylcarbamoyloxymethyl acrylate), 2-(N-methylcarbamoyloxy)-
Mention may be made of carbamoyloxyalkyl acrylates such as ethyl acrylate, 2-(N-ethylcarbamoyloxy)ethyl acrylate, and the like. Lactone-7 acrylate adducts or monoisocyanate-capped lactone-acrylate adducts can also be used as reactive solvents. acrylate,
Neopentyl glycol diacrylate, tetraethylene glycol diacrylate, ester diol-20
4-diacrylate, trimethylolpropane triacrylate, triethylene glycol diacrylate, ester diol 20404 moles of ethylene oxide adduct, alkoxylated ester diol 204 diacrylate, lactone-acrylate adduct reacted with polyfunctional isocyanate. can do. It is also possible to use N-vinylpyrrolidone. Additionally, acrylated oils can be used, such as epoxidized soybean oil and/or the reaction product of epoxy linseed oil and acrylic acid.

The concentration of reactive solvent in the radiation curable coating composition can be from zero to about 70'M%, preferably from about 5 to about 50% by weight f5X.

The concentrations used are selected to achieve the desired application viscosity in the coating composition.

Commonly used solvents include cyclohexanone, methyl isobutyl ketone, tetrahydrofuran, methyl amyl ketone,
ethoxyethyl acetate, etc., and for example methyl isobutyl ketone and 2= of toluene and cyclohexanone.
Mixtures of these solvents are included, such as 2:1 mixtures.

When conventional solvents are used, they range from
Used at a concentration of 9%. The concentration is related to the required viscosity for the specific application and other properties. Generally, conventional or inert solvents are removed or partially removed by evaporation, with or without the use of thermal energy, prior to radiation curing.

In the compositions of the invention, for each mole of polyol, 1.25 to 6 moles of polyfunctional incyane and 0.5 to 8 moles of hydroxy-functional acrylate can be used as reactants.

The coating compositions of the present invention can be cured by ionizing or non-ionizing radiation means including, but not limited to, ultraviolet and electron beam radiation. These curing methods and the equipment that can be used for them are well known to those skilled in the art. The presence of a photoinitiator is preferred when the coating composition is to be cured by non-ionizing radiation. Any known photoinitiator can be used. Examples of suitable photoinitiators include 2,2-diethoxyacetophenone, 2-1 or 3-1 or 4-bromoacetophenone, 3-1 or 4-
Allyl acetophenone, 2-acetonaphthone, benzaldehyde, benzoin, alkylhendiyne ether,
Benzophenone, benzoquinone, 1-chloroanthraginone, p-diacetyl-benzene, 9+10-dibromoanthracene, 9.1.0-dichloroanthracene, 4
．． 4-dichlorobenzophenone, thioxane, 2-chlorothioxanthone, methylthioxanthone, α, α.

α-Trichloro-p-t-butylacetophenone, 4-
Methoxybenzophenone, 3-chloro-8-nonylxanthone, 3-iodo-7-medoxyxanthone, benzaldehyde, carbazole, 4-chloro-47-benzyl-benzophenone, fluorene, fluorenone, 1
, 4-naphthylphenylketone, 2,3-pentanedione, 2,2-di-butoxyacetophenone, dimethoxyphenylacetophenone, flopiophenone, chlorothioxanthone, xanthone, etc., or any mixture thereof. The above table is for illustrative purposes only and is not meant to exclude any suitable photoinitiators known to those skilled in the art. Known to those skilled in the art, and generally the concentration will not exceed 15% by weight of the radiation-curable coating composition.

It is well known to those skilled in the art of photochemistry that photoactivators can be used in combination with said photoinitiators, and that when such combinations are used, synergistic effects may be achieved. . Photoactivators are well known in the art and need no further explanation of what they are and the concentrations at which they are effective. However, examples of suitable photoactivators include methylamine, tributylamine, methyljetanolamine,
-Aminoethylethanolamine, allylamine, cyclo-\xylamine, cyclopentagenylamine, diphenylamine, ditolylamine, trihensylamine, trihensylamine, n-cyclohexyl-ethyleneimine, piperidine, N-methylpiperazine, 2,2-
Examples include dimethyl-1°3-bis(3-N-morpholinyl)flobionyloxypropane.

The compositions of the present invention can also be cured upon exposure to any radiation source that emits actinic radiation at wavelengths within the ultraviolet and visible spectral regions. Suitable radiation sources include water lamps, xenon lamps, carbon arc lamps, sunlight, and the like. Exposure can range from about 1 second or less to 10 minutes or more depending on the particular polymerizable material and photoinitiator used, as well as the distance from the radiation source and the thickness of the coating to be cured. The composition can also be photopolymerized by exposure to electron beam radiation. Generally speaking, the required dose ranges from less than 1 Megarad to 10 Megarad or more.

If desired, various conventional non-basic photonic agents such as silica, talc, glass beads or foams, clays, powdered or finely divided aluminum, cobalt, silver, zinc oxide, iron oxide, cobalt oxide, magnetic Additives such as metals such as oxides) and other viscosity modifiers, rubbers, tackifiers, pigments, etc. can be included in the compositions of the present invention.

The compositions of the present invention have various uses in the field of storage coatings, as binders for magnetic particles used in magnetic recording media, and to improve the flexibility, impact resistance, abrasion resistance and hardness of these compositions. It is particularly suitable for graphic art due to its adhesion to rigid, resilient and flexible substrates such as metals, plastics, rubber, glass, paper, water consolation and ceramics.

EXAMPLES The following examples particularly illustrate the practice of the invention, but they are not intended to limit the scope of the invention in any way.

The following symbols used in the examples have the following meanings.

Dihydroxy-functional polycafrolactone polyol (Union Carbide 1.-
0200).

Preparation of polyol (1) A 500-g reaction flask was equipped with a stirrer, a temperature control mantle equipped with a temperature regulator, a heating mantle, a condenser with a gas outlet, and a gas distribution tube. The flask was charged with diethylene glycol 350y and caprolactone single fi4 monomer 141,9. The mixture was heated to 130°C
and held at that temperature for 30 minutes, during which time nitrogen was sparged. A catalytic solution of 0.002,9 stannous octoate (0.5 d solution of 0.4 d stannous octoate in diethylene glycol lQQIM) was added and the flask heated to "C
i/l: heated. Heating was continued for approximately 2.5 hours after catalyst addition. The reaction was followed by gas chromatography, and the reaction was stopped when the concentration of caprolactone decreased to below 1%. The product had an average molecular Jt of 530.

The procedure for preparing polyol (1) was exactly repeated, except that 448 g of diethylene glycol and 2052 g of caprolactone monomer were used, and the reaction was carried out at 140 DEG C. for 16 hours. The product had an average molecular weight of 830.

Preparation of Polyol (1) 1. The procedure for preparing Polyol (1) was exactly repeated except that 19.1 g of 4-butanediol and 157.69 g of caprolactone monomer were used. The product had an average molecular weight of 830.

Production of polyol (1) 1. The above polyol H except that 594 g of 4-butanediol and 2906 g of caprolactone monomer were used.
The manufacturing procedure was repeated exactly. The product has an average molecular weight of 15
It had 30.

Production of polyol ■ 1.4-butanediol 252! ! The procedure for preparing polyol (1) above was repeated exactly, except that 3248.9 and caprolactone monomer were used and the reaction was carried out at 160° C. for 3.5 hours. Bioacids have an average molecule of 112
It had 50.

Preparation of Caprolactone Adduct 1 A 50 gallon glass-lined reactor equipped with an agitator, temperature regulator, and nitrogen/air inlet and outlet tubing was used as the reaction vessel. The ε-caprolactone was dried by contacting it with molecular seeds. The dried ε-caprolactone was then dried by contacting it with molecular seeds.

Next, the dried ε-caprolactone 242 bond and monomethyl ether of hydroquinone 1001 dissolved in a small amount of ε-caprolactone were introduced into a reaction vessel.
The system was sparged with nitrogen during this time. When the temperature reached 100℃, change the nitrogen sparging to a nitrogen atmosphere,
Air sparging was started. 2-Hydroxyethyl acrylate 124 bond and stannous octoate i o o pp
A mixture of m was added. The reaction temperature was increased to 125°C and the reaction mixture was kept at this temperature for 12 hours. The reaction mixture was then cooled to room temperature (approximately 25° C.) and collected as residual product. The product has a hydroxyl number of 1791 and an acid number of 3.
．． 13, Brookfield viscosity 76 centiboaz (2
5° C.) and a water content of 135 ppm.

Control Example A: 2 moles of 2-ethylhexyl acrylate, 2 moles of inphorone diisocyanate in a 500a four neck round bottom flask equipped with an air condenser, mechanical stirrer, addition funnel, thermometer, heating mantle and dry air atmosphere. and dibutyltin dilaurate. The mixture was heated to 55 DEG C. and 2 moles of polyol (2) were added dropwise through the addition funnel. After the addition of polyol 1 was complete, 2 moles of hydroxyethyl acrylate were added dropwise through the dropping funnel. The reaction mixture was kept at 55-60°C.

Example 1 2-ethylhexyl acrylate 15Q, 9. 129g,
0.5 g of dibutyltin dilaure and 01 g of 2,6-di-t-butyl-4-methylphenol were added.

The mixture was heated to 55° C. and 154 g of polyol (1) was added dropwise through the dropping funnel. After the addition of polyol (1) was complete, a mixture of caprolactone (99.8 g) and 2-hydroxyethyl acrylate (33,7,!i') was added dropwise through the dropping funnel. The reaction mixture was maintained at 55-60°C until the isocyanate level was below about 0.2% by weight as determined by titration with dibutylamine.

Example 2 1,6-hexanethiol diacrylate) 1 in a flask
5 (11 isophorone diisocyanate 129I, dibutyltin dilaurate and 2,6-sheet t-butyl-4-
The procedure of Example 10 was repeated exactly except that 0.5 g of methylphenol was charged.

154 g of Polyol I was added to the heated mixture.

After the polyol addition is complete, the caprolactone adduct [(9
9,8#) and 2-hydroxyethyl acrylate) (33
, 7g) was added, Example 1
Example 3 Following the procedure described in Example 3 -145 g of 2-ethylhexyl acrylate was added to the flask.
The procedure of Example 10 was repeated exactly, except that 131 g of inphorone diisocyanate, dibutyltin dilaurate, and 0.5 g of 2,6-di-t-butyl-4-methylphenol were charged. Add polyol to the heated mixture■
106 g of the solution was added. After the polyol addition was complete, 250 g of a mixture of caprolactone adduct I (227 g) and 2-hydroxyethyl acrylate (23 g) were added and the procedure described in Example 1 was continued.

Example 4 138 g of 2-ethylhexyl acrylate in 7 flasks,
The procedure of Example 10 was repeated exactly, except that 105 g of toluene diincyanate, dibutyltin dilaurate, and 0.5 y of 2,6-di-t-butyl-4-methylphenol were charged. 106 g of Polyol I was added to the heated mixture. After the polyol addition was complete, 250 g of a mixture of caprolactone adduct I (227F) and 2-hydroxyethyl acrid (23 g) were added and the procedure described in Example 1 was continued.

Example 5 177 g of 2-ethylhexyl acrylate in a flask,
The procedure of Example 10 was repeated exactly, except that inphorone diincyanate 110,9° dibutyltin dilaurate and 0.5 g of 2,6-di-t-buty/I/-4-methylphenol were charged. 133 g of polyol-yl was added to the heated mixture. After the polyol addition was complete, 172 g of caprolactone adduct 1 was added and the procedure described in Example 1 was continued.

Example 6 145 g of hexanediol diacrylate in a flask,
Inphoron diincyanate 131, li'.

The procedure of Example 10 was repeated exactly except that 5 g of dibutyltin dilaurate and 2,6-di-t-butyl-4-methylphenol were charged. To the heated mixture was added 106 g of polyol (1). After the addition of the polyol was completed, a mixture of caprolactone adduct (227 &) and 2-hydroxyethyl acrylate (23 g) was added.
g and continued the Example 10 procedure.

Example 7 188 g of 2-ethylhexyl acrylate in a flask,
1 luene diisocyanate 94,9, dibutyltin dilaurate and 2,6-di-6-1-butyl-4-methylphenol 0.5,! The procedure of Example 10 was repeated exactly except that i' was charged.

95 g of Polyol I was added to the heated mixture.

2 of caprolactone adduct I after completion of addition of polyol
45 g was added and the procedure described in Example 1 was continued.

Example 8 2-ethylhexyl acrylate]28I in a flask,
110 g of inphorone diincyanate, dibutyltin dilaurate and 2,6-di-t-butyl-4-methyA.
Example 1 except that phenol 0.5 fi was charged.
I repeated the steps exactly. 133 g of polyol (1) was added to the heated mixture. After the addition of polyol Ⅰ was complete, 5J9 of caprolactone adduct I was added and the procedure described in Example 1 was continued.

Example 9 128 g of 2-ethylhexyl acrylate in a flask,
The procedure of Example 1 was repeated exactly, except that 110 g of isophorone diincyanate, dibutyltin dilaurate, and 0.59 g of 2,6-di-t-butyl-4-methylphenol were charged. Polyol (1) 133I was added to the heated mixture. 58 of the caprolactone adduct (■) after the addition of the polyol (■) is complete. Example 1
Continued the procedure described in.

Example 10 160 g of 2-ethylhexyl acrylate in a flask,
Isophorone diisocyanate 10. ! i'.

The procedure of Example 1 was repeated exactly, except that dibutyltin dilaurate and 2,6-di-t-butyl-4-methylphenol o,sg were charged. 208 g of polyol (2) was added to the heated mixture. Polyol ■
After the addition of caprolactone adduct Ⅰ, 58F was added and the procedure described in Example 1 was continued.

Example 11 165 g of 2-ethylhexyl acrylate in a flask,
The procedure of Example 1 was repeated exactly, except that 88 g of isophorone diisocyanate, dibutyltin dilaurate, and 0.5 g of 2,6-di-t-butyl-4-methylphenol were charged. 250 g of polyol ① of the heated mixture was added. After the addition of polyol 1 was complete, 589 of caprolactone adduct I was added and the procedure described in Example 1 was continued.

Example 12 In a flask, 150 g of cyclohexanone, 129 g of inphorone diisocyanate, dibutyltin dilaurate, and 0.0 g of 2,6-di-t-butyl-4-methylphenol were added. !
M? The procedure of Example 10 was repeated exactly, except that . 154 g of Polyol I was added to the heated mixture. After the polyol addition was complete, 68 hours of caprolactone additive I was added and followed as described in Example 1 for 11 hours.

Example J3 Cyclohequinone 146#, Inphorone diisocyanate 133.9. Dibutyltin dilaurate and 2,6-di-t-butyl-4-methylphenol 0.
The procedure of Example 1 was repeated exactly except that 59 was added. Add polio-#[)] to the heated mixture 06
I! i+ was added. After the polyol addition was complete, a mixture of caprolactone adduct I (106 g) and hydroxyethyl acrylate (23 g) 1249 was added and the procedure described in the example was continued.

Example 14 A glass reactor equipped with a stirrer, a thermometer, and an air inlet and outlet was charged with the following ingredients: Table I N-vinylpyrrolidone 250g ---Ibornyl acrylate 250.9 Ethylene glycol dimethyl acrylate 250p 250g Alloocymene 1,
29 1.2y dibutyltin dilaure) 1.2.47 L7g These ingredients were heated to 61°C 1-, caprolactone adduct ■
was added over 30 minutes. Then 65.3% polyol 4639 was pre-dried by heating at 135° C. for about 2 hours under nitrogen sparge and added over a period of 1 hour. When the addition was complete, 124y of caprolactone adduct I was added over 10 minutes. The temperature was maintained at about 65-70°C during this addition and for the next 25 minutes of reaction time. After this time, the vinyl methyl ether of hydroquinone 30
．． 9 was added.

After cooling the products of Runs A and B to room temperature, the free incyanate content n was determined and found to be 0.14% for Run A and 0.20% for Run B. Experiment A
The residual products of and B have viscosities of 8 and 460 Cp (
In each case, about 1% by weight of 2,2-dimethoxy-2-phenylacetophenone [Irgacure 651, manufactured by Civer Geigy] was added to the coating agent before UV curing. added to. Apply the liquid coating to silicone release paper using a suitable wire-wound rod to a thickness of 1 to 1
An o-mil cured film was produced. The applied coating was transferred to a Linde D.
Cured using a BBG 3-M curing unit. If the film is hardened on both sides, it will be completely cured (thro
It is necessary to obtain ugbcure). All samples were cured under nitrogen atmosphere.

After curing, the film was removed from the release paper 7 and the mechanical film properties were measured.

The table shows the tensile strength (psi) and elongation (%) of the cured coating, as well as the viscosity of the composition.

Table ■ Control example A 1000 65 3200 1 670 100 2230 2 3690 30 3880 3 1115 55 1075 4 850 90 1310 5 4-05 55 11.35 6 4200 10 1350 7 335 30 670 8 1o50 75 2t90 9 1125 85 1970 10 425 55 1725 11 295 GO1975 12100066--* 13 410 50 --43 *State: 1. It will be appreciated by those skilled in the art that properties will vary depending on the selection of the amounts of reactive solvents and other additives used.

Patent Applicant: Union, Carbide Corporation: '-----: Agent Roku Takagi: Division; I□□□□ Agent Fumi Shio Takagi 1st Supplement 11': Showa Me! Indication of the patent case of July 3, 2007, 1934, 8th edition, No. 134, No. 1Z
Name of Eyf Coating IZ (7) ffJ It
IB-Eight supplementary person [person who carries out a trial] Relationship to the incident nt? Applicant A fF Koniono, Myo-Bai F, Koho 0 Regen Agent Personal Address East Radical Flood 1” Convex I Convex 1j-8th No. 6
Mr. Murao゛°1' Name Patent Attorney (6228) I! (1
Book 6-i.

Address 18th 643 Tsukeho Hill "81"Ll: (6"63) Ii * J-
Cao°! I supplementary IF instruction with 11 - Shaoshan - u, (- month - +
-Procedural amendments February 6th, 2015 Patent section length n Shinsei Kodono 1 (Display of 1 Showa, 7th year of 1999! 4 fif petition July 2nd issue R issue 'Bamboo name 7) Sekkai tft Cornuin 7"r-4tQ h IU8 to supplement"■- to 1-
Relationship to the case nfr applicant χ fken ni/1
Bere Baito "', J-Ho0V-Nyo/Agent Address p, Tobu Port/Nishimobashi IJ-18-6 Ri Doho Hill' 1 Name Patent Attorney 47 (6228) Takagi Rokube 1st residence Toku "East V Miyako [) Nishi-Shinbashi Yu J-Eye 18th 6th Ri Sumire 1 Hill Supplement I ■ Order's 11 E 1-4 Eyebrow - @←-Ro ■--
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1. Contents of amendment 1. Between the 4th and 3rd lines from the bottom of page 7 of the Meitetsusho, the following information is added.

“U.S. Patent No. 3,700,643 (Reissue No. 29.
No. 131) Specifications =, g, the coating composition is +3
Self listed. These coating compositions include, of course, the liquid ratio of polycaprolactone polyol to acrylic acid or polycaprolactone polyol to "H4'd incyanate to hydroxyalkyl acrylate,"
i.Cut 1 paddy. The patent specification: I'lj- is a polycaprolactone polyol having at least 11 M I, 1 #1 hydroxyl groups reacted with an acrylic I to form a polycasilolactone capped by an acrylate, I+l Polyisocyanates can also be combined with hydroxyalkyl acrylates and polycaprolactone polyols to produce acrylate-capped polycaprolactone/urethanes.1 It is stated that the compounds can be used as coating compositions or they can be mixed with other compounds to form coating compositions.

U.S. Pat. No. 4,188,472 discloses that a lactone is totally reacted with an ester having an acrylic group or an α-positioned acrylic group and one or two hydroxyl groups,
Then, by reacting the dough thus produced with a number of in7 anates, the resulting 4 fats are produced. The coating has a low viscosity of 'C'+7 and is designated as 1/3 for use in local coating operations as well as for operations where U-curing is desired.

However, the composition used in the radiation-resistant coating composition can be easily applied to the substrate using conventional coating techniques without the use of diluents. It is desirable to have a viscosity that is low enough so that it can be applied to a plate.

The coating composition for the 1π and 1ζ coatings should cure and provide good physical properties for the 1ζ coating. Prior Art Le 11. Naturally, it lacks the combination of low viscosity, high tensile strength and good extensibility. ” 2 Remove 141 from lines 7 to 9 of page 51, “Next, old... drying.” Shimazu-0

Claims (1)

Claims: 1. A composition suitable for use as a curable coating, characterized in that it comprises a reaction product of a polyol, a polyfunctional isocyanate, and a lactone-acrylate adduct. 2. The composition according to claim 1, wherein the reaction product contains hydroxyalkyl acrylate. 3. The composition of claim 1 selected from the group consisting of polyol polyether polyol, polycaprolactone polyol, polyester polyol, acrylic polyol, vinyl polyol, polymer/polyol or mixtures thereof. 4o polyether polyol, propylene oxide polyol, ethylene oxide polyol, propylene oxide polyol capped with ethylene oxide,
4. The composition of claim 3 selected from the group consisting of ethylene oxide/propylene oxide copolymers, tetramethylene oxide copolymers, tetramethylene oxide, and polymers/polyols. 5. The composition according to claim 1, wherein the polyol is a polymer polyol. 6. The composition according to claim 1, wherein the polyol is polyepsilon caprolactone polyol. 7. The composition according to claim 1, wherein the polyol is a polyester polyol. 8. The composition according to claim 1, wherein the polyol is an acrylic polyol. 9. The composition according to claim 1, wherein the polyol is a vinyl polyol. 10, polyfunctional isocyanate and 2.4-) lylene diisocyanate), 2.6-) lylene diisocyanate,
Isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate, di(2-incyanatoethyl)
~bicyclo(2,2,1) hept-5-ene-2,3
-dicarboxylate, 3.5.5-triethyl-1-
incyanato-3-isocyanato-methylcyclohexane, 1,6-hexamethylene diisocyanate, m- and p-xylene diisocyanate, cyclohexane-1
, 4-diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, tetramethylene diisocyanate, cyclobencicine-1,3-diisocyanate),
1,3-diincyanate, 1,4-xylylene diisocyanate, 1,5-naphthalene diisocyanate, m
-phenylene diisocyanate, p-phenylene diisocyanate, hexamethylene diisocyanate, 3,3
'-dimethyl-4,4'-diphenylmethane diisocyanate), 4,4'-diphenylene diisocyanate, 3
．． 3'-Dimethoxy 4,4'-dimethyl 4,4'-biphenylene diisocyanate, durenidisocyanate, 1-7 enoxy 2,4-7enylene diiso2anate, 1-t-butyl-2,4-phenylene diisocyanate, 2t2, 4-) Limethyl-xamethylene diincyanate, 1,3.5-benzene triincyanate, 2.4.6-) Lutriincyanate toluene or mixtures thereof.Claims 1
Compositions as described in Section. 11. The composition according to claim 1, wherein the lactone-acrylate adduct is produced by reacting a lactone with a hydroxyalkyl acrylate. 12, the lactone has the following formula: (wherein R' is independently hydrogen or a carbon atom +1 to 12
and I is 4 to 7. 13. The composition according to claim 12, wherein the lactone is ε-caprolactone. 14, hydroxyalkyl acrylate, 2-hydroxyethyl acrylate, hydroxyalkyl acrylate, human xybutyl acrylate, 2-hydroxy-
12. A composition according to claim 11 selected from 3-chloropropyl acrylate, 2,3-dihydroxyfurobyl acrylate, or mixtures thereof. ]J. The composition according to claim 14, wherein the hydroxyalkyl acrylate is hydroxyethyl acrylate. 16. The composition according to claim 2, wherein the hydroxyalkyl acrylate is as defined in claim 14. 2. The composition of claim 1 containing 1 reactive solvent. 1B, the reactive solvent has the formula: The substituent can be alkoxy, hydroxy, cyano or amino, or R9 can be carbamoyloxyalkyl which can be N-alkyl substituted. Composition. 19. The composition according to claim 17, wherein the reactive solvent is a polyfunctional alkyl acrylate. 20, the reactive solvent is 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tetramethylene glycol diacrylate, ester di-
20. The composition of claim 19, which is a diarylate of #-204-diacrylate, trimethylolpropane triacrylate, triethylene glycol diacrylate, alkoxylated ester diol 204, or a mixture thereof. 21. The composition according to claim 17, wherein the reactive solvent is N-vinylpyrrolidone. 22. The composition according to claim 19, wherein the reactive solvent is a lactone-acrylate adduct reacted with a polyfunctional incyanate. 23. The composition according to claim 1, which contains a non-reactive solvent. 24. The composition according to claim 23, wherein the solvent is cyclohexanone, toluene, methyl imbutyl ketone, tetrahydrone, methyl amyl ketone, ethoxyethyl acetate, and mixtures thereof. 2. A cured coating made from the composition of claim 1 or 17 or 23.